Supplementary Material
Characterization of Trace Contaminants in Syngas from the
Thermochemical Conversion of Biomass
S. Kent Hoekman*1, Curtis Robbins1, Xiaoliang Wang1, Barbara Zielinska1,
Dennis Schuetzle2 and Robert Schuetzle3
1Division
of Atmospheric Sciences, Desert Research Institute (DRI), 2215 Raggio Parkway,
Reno, NV 89512
2Renewable
3Pacific
Energy Institute International (REII), McClellan, CA 95652
Renewable Fuels and Chemicals, McClellan, CA 95652
Part 1: Protocols for Sampling and Analysis of Syngas………………………………………2
Part 2: Results from Analysis of Syngas Samples Collected from Synterra IBR……….….15
Reference List...…………………………………………………………………………………22
Part 1: Protocols for Sampling and Analysis of Syngas
A. Canister Samples
1. Canister preparation and collection
Prior to use, electro-polished canisters are cleaned by alternating evacuation and flushing through
seven cycles with humid, ultra high purity (UHP) air at 140 ºC. Ten percent of the cleaned canisters
are then pressurized with humid UHP air, allowed to equilibrate overnight, then analyzed by gas
chromatography with flame ionization detection (GC/FID). For blank samples, each individual target
compound should be present at concentration less than 0.2 ppbv; total non-methane hydrocarbon
concentration should be less than 10 ppbC. Before shipping to a field site for use, the canisters are
evacuated in the laboratory by connection to a vacuum line. When collecting syngas, the evacuated
canister is opened by a solenoid valve, and the flow is regulated through a critical orifice.
2. Canister Analysis (for C2-C11)
For analysis of VOCs, a gas chromatography/mass spectrometry/flame ionization detector
(GC/MS/FID) method is employed, based upon guidance provided by EPA Method TO-15.1 The
integrated GC/MS/FID system includes a Lotus Consulting Ultra-Trace Toxics sample preconcentration system built into a Varian 3800 GC instrument with a FID, coupled to a Varian Saturn
2000 ion trap mass spectrometer. The Lotus pre-concentration system consists of three traps. Midand heavier weight hydrocarbons are collected on the front trap consisting of 1/8” nickel tubing
packed with multiple adsorbents. Trapping is performed at 55 ºC and eluting is performed at 200 ºC.
The rear traps consist of an empty 0.040” ID nickel tubing (for light hydrocarbons) and a cryofocusing trap (for mid and higher weight hydrocarbons isolated in the front trap). The cryo-focusing
trap is built from 6’ x 1/8” nickel tubing filled with glass beads. Trapping in both rear traps occurs at
-180 ºC and eluting at 200 ºC. Light hydrocarbons are deposited onto a Varian CP-Sil5 column (15m
x 0.32mm x 1µm) plumbed to a column-switching valve within the GC oven, then to a Chrompack
Al2O3/KCl column (25m x 0.53mm x 10µm) leading to the flame ionization detector (FID) for
quantification of light hydrocarbons (C2-C4). The mid-range and heavier hydrocarbons cryo-focused
in the rear trap are deposited onto a J&W DB-1 column (60m x 0.32mm x 1µm) connected to an ion
trap mass spectrometer. The GC initial temperature is 5 ºC, held for approximately 9.5 minutes, then
ramped at 3 ºC/min to 200 ºC for a total run time of 80 minutes.
2
Calibration of the system is conducted with a mixture that contains commonly found hydrocarbons
(75 compounds from ethane to n-undecane, purchased from Air Environmental) in the range of 0.2 to
10 ppbv. Three point external calibrations are run prior to analysis, and one calibration check is run
every 24 hours. If the response of an individual compound is more than 10% off, the system is
recalibrated.
Replicate analyses are conducted at least 24 hours after the initial analyses to allow re-equilibration
of the compounds within the canisters. All replicate analyses are flagged in the project database. The
data processing program extracts these replicates and determines a replicate precision. Replicate
analysis is important because it provides a continuous check on all aspects of each analysis, and
highlights analytical problems before they become significant.
Method detection limit (MDL) is determined as recommended by the EPA Method TO-15 (according
to the Code of Federal Regulations, 40 CFR 136 Appendix B). Briefly, seven consecutive replicate
measurements of the compounds of interest at concentrations near (within a factor of 5) the expected
detection limits are made, and the standard deviations for these 7 replicate concentrations are
calculated. The MDL is obtained by multiplying these standard deviations by 3.14 (i.e. the Student’s
t-value for 99 percent confidence for 7 values). In general, MDLs for VOC measurements are 0.1 –
0.2 ppbv.
3. Canister Analysis of Permanent Gases (CO, CO2, N2, CH4, H2)
3a. Methane, Carbon Monoxide, and Carbon Dioxide
Methane (CH4), carbon monoxide (CO) and carbon dioxide (CO2) are measured from canister
samples using GC/FID (Shimadzu GC-17A). Since the FID does not respond to CO and CO2, these
species are converted to methane by a methanator, positioned immediately after the GC column, but
ahead of the detector. The methanator comprises a firebrick powder impregnated with nickel catalyst,
through which a stream of hydrogen gas flows continuously at ~450 C.
For compound separation, a 20-ft x 1/8-in. inner-diameter (i.d.) column, packed with 60/80 mesh of
Carboxen 1000 (Supelco) is used. This column provides sufficient separation between CH 4 and CO
without retaining CO2. Five-ml samples are injected using a constant volume loop. An initial column
temperature of 35 °C is held for 8-min., followed by a gradient of 15 °C/min to a final temperature of
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200 °C. Response factors are determined by calibrations with gaseous standard mixtures (Scott
Specialty Gases or AGA Specialty Gases, NIST-traceable) containing CO, CO2 and CH4 in zero air.
The minimum detection limits are 0.06 ppmv for CO, 0.2 ppmv for CH4, and ~3 ppmv for CO2
(MDLs determined as described above). The precision of measurements is generally better than 10%.
3b. Hydrogen and Nitrogen
Hydrogen (H2) and nitrogen (N2) concentrations are measured using a SRI 8610C gas chromatograph
with a 0.5 ml sample loop and a thermal conductivity detector. A SRI Molecular Sieve 13x (6 ft x 1/8
in ID) GC column is used. The initial GC oven temperature is 40°C, followed by a temperature ramp
of 50°C/min to 200°C and final hold of 6.8 minutes, giving a total run time of 10 minutes.
A single stock calibration standard was obtained from Airgas containing a blend of H2 (50.04%
±1%), CO (19.98% ±1%), CO2 (19.98% ±1%), and CH4 (10% ±1%). Lower calibration levels were
prepared by quantitatively diluting the stock gas with ultra high purity N2 into 6-liter stainless steel
canisters. H2 calibration levels were 7.48%, 20.28%, 30.17%, and 50.04%. N2 standards were
prepared from an ultra high purity (UHP) N2 sample mixed with helium (He).
B. Carbonyl Samples
1. Carbonyl Collection
Carbonyl compounds are collected by drawing air through silica gel Sep-Pak® cartridges
impregnated with acidified 2,4-dinitrophenylhydrazine (DNPH), available commercially from
Waters, Inc. The resulting products (hydrazones) in the cartridges are measured in the laboratory
using high performance liquid chromatography (HPLC). The dilution sampler system used for
carbonyl collection includes check valves, solenoid valves and a pump to enable flow control and
measurement for each cartridge. Used cartridges are immediately removed from the sampler,
plugged, put into vials, and stored in a refrigerator until they are returned to the laboratory (in a
cooler) for final analysis.
2. Carbonyl Analysis
After sampling, the DNPH Sep-Pak® cartridges are eluted with 2-mL acetonitrile to remove the
hydrazone products produced during sampling of carbonyl compounds. An aliquot of the eluent is
transferred into a 2-mL septum vial and injected with an autosampler into a high performance liquid
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chromatograph (HPLC; Waters 2690 Alliance System with 996 Photodiode Array Detector) for
separation and quantification of the hydrazones.2 The chromatographic conditions are as follows:
Polaris C18-A 3µm 100 x 2.0 mm HPLC column, flow rate of 0.2 ml/min, injection volume of 2.0
µl, solvent A: water, solvent B: acetonitrile. The HPLC program is: 60% A, 40% B for 0.02 min.,
50% A and 50% B over 15 min., 30% A and 70% B over 6 min., and 100% B over 1 min., final hold
at 100% B for 1 min. Total run time is 30 min. C1 through C7 carbonyl compounds are analyzed,
including the following: formaldehyde, acetaldehyde, acetone, acrolein, propionaldehyde,
crotonaldehyde, methyl ethyl ketone, methacrolein, butyraldehyde, benzaldehyde, glyoxal,
valeraldehyde, m-tolualdehyde, and hexanaldehyde. The original carbonyl concentrations in the
syngas (in units of ppbv) are computed from the amounts measured after blank correction, and after
accounting for the volume of syngas sampled. MDLs are determined according to the method
described above for VOC, and are generally in the range of 0.1-0.2 ppbv.
C. Tenax C8-C20 VOC Samples
1. Tenax Collection
Tenax sampling and analysis is employed for compounds that are too heavy to be quantitatively
retrieved from canisters. [These higher MW VOCs are sometimes called semi-volatile organic
compounds (SVOCs).] Prior to use, the Tenax-TA solid adsorbent is cleaned by a Dionex
Accelerated Solvent Extractor (ASE) method using hexane/acetone mixture (4/1 v/v), and dried in a
vacuum oven at ~80 ºC. The dry Tenax is packed into Pyrex glass tubes (4 mm i.d. x 15 cm long;
each tube containing 0.2 g of Tenax) and is thermally conditioned for four hours by heating in an
oven at 300 ºC under a nitrogen purge (25 mL/min N2 flow). Approximately 10% of the pre-cleaned
Tenax cartridges are tested by GC/MS for quality assurance prior to sampling. After cleaning, the
Tenax cartridges are capped tightly using clean Swagelok caps (brass) with graphite/vespel ferrules,
placed in metal containers with activated charcoal on the bottom, and kept in a clean environment at
room temperature.
As described above for the DNPH cartridges, flow control and measurement is done for each
individual Tenax cartridge during use. After use, the exposed cartridges are removed, immediately
plugged with Swagelok caps, and stored in the same metal containers with activated charcoal on the
bottom. The exposed cartridges are stored under refrigeration until they are returned to the laboratory
in a cooler containing blue ice.
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2. Tenax Analysis
The Tenax samples are analyzed by a thermal desorption-cryogenic pre-concentration method,
followed by high-resolution gas chromatographic separation and mass spectrometric detection
(GC/MS) of individual compounds.3 A Gerstel ThermoDesorption System (TDS) unit, equipped with
a 20 position autosampler is used for these analyses. This TDS unit is coupled to a Varian Saturn
2000 GC/MS system, equipped with sample desorption and cryogenic pre-concentration capabilities.
A DB-1 capillary column (60 m x 0.32 mm i.d., 0.25 µm film thickness; J&W Scientific, Inc.) is
used to achieve separation of the target species. The GC initial temperature of 30 °C is held for 3min., then increased to 250 °C at 5 °C/min., and held for 3-min. for a total run time of 50 min.
For calibration purposes, Tenax cartridges are spiked with a methanol solution of standard
hydrocarbons, prepared from high-purity commercially available C8-C20 aliphatic, oxygenated, and
aromatic hydrocarbons. The solvent is then removed with a stream of He (2 min, 100 mL/min at
room temperature) and the Tenax cartridges are thermally desorbed into the GC system. Three
concentrations of each standard compound are employed and two replicate sample injections per
calibration level are made. Area response factors per nanogram of compound per Tenax cartridge are
calculated by the instrument software for each concentration. All response factors are recorded in the
software program and the mean or median value is taken. The original concentrations of SVOCs in
the syngas (expressed in units of µg/m3) are computed after accounting for the volume of syngas
sampled. MDLs are determined as described above for VOC, and are generally in the range of 0.010.02 µg/cartridge.
D. Filter Packs
1. Filter Sample Collection
No single filter medium is appropriate for all desired analyses, so it is necessary to sample on
multiple substrates for chemical speciation. Filter packs containing 47-mm diameter Teflonmembrane, quartz fiber, and cellulose filters are used for syngas sampling and analysis. All filter
batches are conditioned and acceptance tested prior to use in sampling. Two percent of filters from
each batch are subjected to identical blank analyses, to ensure that they are sufficiently clean before
use in actual sampling. The following three types of filters are used:
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1. Teflon-membrane filters are used for measurement of mass and elemental concentrations.
These filters are obtained from Pall Corporation (Part No. R2PJ047) or Whatman Inc.
(Part No. 7592-104). They have a 2 µm pore size, and are used with polymethylpropylene
(PMP) support rings.
2. Quartz fiber filters are used for determination of carbon fractions and ions in the
particulate phase. These filters are obtained from Pall Corporation (Part No. 7202) or
Whatman Inc. (Part No. 1851-047). They have an approximate thickness of 432 µm, fiber
diameter of 0.6 µm, and packing density of 0.038 g/cm3.
3. Cellulose fiber filters are placed behind the more efficient particle-collecting filters
(Teflon-membrane and quartz fiber). They are impregnated with gas-absorbing
compounds, and are used to capture ammonia (with citric acid impregnation), acidic
gases (with K2CO3 impregnation), and H2S (with AgNO3 impregnation). These filters are
obtained from Whatman Inc. (31ET and 41), and have a thickness of 0.50 mm.
2. PM Mass by Gravimetric Analysis
Unexposed and exposed Teflon-membrane filters are equilibrated at a temperature of 21.5 ± 1.5 °C
and a relative humidity of 35 ± 5% for a minimum of 24 hours prior to weighing. Weighing is
performed on a Metter Toledo MT5 electro-microbalance with ±0.001 mg sensitivity. The charge on
each filter is neutralized by exposure to a 210Po ionizing source for 30 seconds or more prior to the
filter being placed on the balance pan. The balance is calibrated with a series of three Class 1 weights
(50, 100, and 200 mg) and the tare is set prior to weighing each batch of filters. After every 10 filters
are weighed, the calibration and tare are re-checked. If the results of these performance tests deviate
from specifications by more than ±5 g, the balance is re-calibrated.
Replicate weights are determined on 100% of the filters before sampling (initial weights or preweights), and on 30% of the filters after sampling (final weights or post-weights) by an independent
technician. Replicate pre-sampling (initial) weights must be within ± 0.010 mg of the original
weights. Replicate post-sampling (final) weights on lightly-loaded samples (i.e., less than 1 mg) must
be within ± 0.015 mg. Post-sampling weights on heavily loaded (i.e., greater than 1 mg) samples
must be within 2% of the net weight. Pre- and post-weights, check weights, and re-weights (if
required) are recorded on data sheets as well as being directly entered into a database via an internet
connection.
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3. Elements by X-Ray Fluorescence
Individual elements are analyzed on Teflon-membrane filters using a PANalytical Epsilon 5, energy
dispersive x-ray fluorescence (ED-XRF) analyzer.4 The emissions of x-ray photons from the sample
are integrated over time and yield quantitative measurements for 51 elements ranging from aluminum
(Al) through uranium (U), and semi-quantitative measurements of sodium (Na) and magnesium
(Mg). A spectrum of x-ray counts versus photon energy is acquired and displayed during analysis,
with individual peak energies corresponding to each element, and peak areas corresponding to
elemental concentrations. The advantages of XRF analysis include high sensitivity for a large
number of elements, the ability to analyze small sample quantities, and the non-destructive nature of
the analysis.
The source of x-rays in the PANalytical Epsilon 5 analyzer is a side-window, liquid-cooled, 100
KeV, 24 milliamp gadolinium anode x-ray tube. X-rays are focused on one of 11 secondary targets
(Al, Ca, Ti, Fe, Ge, Zr, Mo, Ag, Cs, Ba, Ce) which in turn emit polarized x-rays to excite a sample.
X-rays from the secondary target or the tube are absorbed by the sample, exciting electrons to higher
level orbitals. As the electrons return to their ground state, photons are emitted which are
characteristic of the quantum level jumps made by the electron; the energy of the emitted photons
are, therefore, characteristic of the elements contained in the sample. The fluoresced photons are
detected in a solid state germanium x-ray detector. Each photon that enters the detector generates an
electrical charge whose magnitude is proportional to the photon's energy. The number of these
photons is proportional to the number of atoms present. Ten separate XRF analyses are conducted on
each sample to optimize detection limits for the specified elements. The ED-XRF system is
calibrated using Micromatter (Arlington, WA) thin film standards. Multielement standards are
analyzed daily to monitor for any instrument drift. Method detection limit (MDL) is defined as 3
times the standard deviation of multiple measurements of a laboratory blank filter.
4. Carbon Analysis by Thermal/Optical Reflectance/Transmittance (TOR/TOT)
The thermal/optical reflectance and transmittance (TOR/TOT) method measures organic carbon
(OC) and elemental carbon (EC) on filter samples.5 This method is based on the principle that
different types of carbon-containing particles are converted to gases under different temperature and
oxidation conditions. The different carbon fractions from TOR/TOT are useful for comparison with
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other methods, which are specific to a single definition for organic and elemental carbon. The seven
carbon fractions measured by the DRI Model 2001 Thermal/Optical Carbon Analyzer are the
following:
1) OC1: Carbon evolved in a helium atmosphere at temperatures between ambient and 140 °C
2) OC2: Carbon evolved in a helium atmosphere at temperatures between 140 and 280 °C
3) OC3: Carbon evolved in a helium atmosphere at temperatures between 280 and 480 °C
4) OC4: Carbon evolved in a helium atmosphere between 480 and 580 °C
5) EC1: Carbon evolved in an oxidizing atmosphere at 580 °C
6) EC2: Carbon evolved in an oxidizing atmosphere between 580 and 740 °C
7) EC3: Carbon evolved in an oxidizing atmosphere between 740 and 840 °C
The thermal/optical reflectance carbon analyzer contains a thermal system and an optical system. The
thermal system consists of a quartz tube placed inside a coiled heater. Current through the heater is
controlled to attain and maintain pre-set temperatures for given time periods. A portion of a quartz
filter is placed in the heating zone and heated to different temperatures under non-oxidizing and
oxidizing atmospheres. The optical system consists of a He-Ne laser, a fiber optic transmitter and
receiver, and a photocell. The filter deposit faces a quartz light tube so that the intensity of the
reflected laser beam can be monitored throughout the analysis.
As the temperature increases from ambient (~25 °C) to 580 °C, organic compounds are volatilized
from the filter in a non-oxidizing (He) atmosphere while elemental carbon is not oxidized. When
oxygen is added to the helium at temperatures greater than 580 °C, the elemental carbon burns and
enters the sample stream. The evolved gases pass through an oxidizing bed of heated manganese
dioxide where they are oxidized to carbon dioxide, then across a heated nickel catalyst, which
reduces the carbon dioxide (by reaction with hydrogen) to produce methane (CH4). The methane is
then quantified with a flame ionization detector (FID).
The laser light for reflectance and transmittance is continuously monitored throughout the analysis
cycle. The negative change in laser signal is proportional to the degree of pyrolytic conversion from
OC to EC that takes place during OC analysis. After O2 is introduced, the laser signal increases
rapidly as the light-absorbing carbon is burned off the filter. The carbon measured after the
reflectance attains the value it had at the beginning of the analysis cycle is classified as EC. This
adjustment for pyrolysis (i.e., optical pyrolysis [OP]) in the analysis is significant, and cannot be
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ignored. OC and EC are calculated as OC = OC1 + OC2 + OC3 + OC4 + OP and EC = EC1 + EC2 +
EC3 - OP.
The carbon analyzer system is calibrated by analyzing samples of known amounts of CH4, CO2,
sucrose, and potassium hydrogen phthalate (KHP). The FID response is ratioed to a reference level of
CH4 injected at the end of each sample analysis. Performance tests of the instrument calibration are
conducted at the beginning and end of each day's operation. Intervening samples are re-analyzed
when calibration changes of more than ±10% are found. Known amounts of American Chemical
Society (ACS) certified reagent grade crystal sucrose and KHP are committed to carbon analysis as a
verification of the OC fractions. Fifteen different standards are used for each calibration.
5. Filter Extraction
Water-soluble cations and anions are obtained by extracting a quartz-fiber filter in 15 mL of
deionized-distilled water (DDW). The filter is placed in a 16 x 150 mm polystyrene extraction vial
with a screw cap (e.g., Falcon #2045). Each vial is labeled with a bar code sticker containing the
filter ID code. The extraction tubes are placed in tube racks, and the extraction solutions are added.
The extraction vials are capped and sonicated for 60 minutes, shaken for 60 minutes, then aged
overnight to assure complete extraction of the deposited material into the solvent. The ultrasonic bath
water is monitored to prevent temperature increases from the dissipation of ultrasonic energy in the
water. After extraction, these solutions are stored under refrigeration prior to analysis.
6. Water-Soluble Particulate Anion Analyses
Water-soluble particulate anions (Cl-, NO2-, NO3-, PO43-, and SO42-) are collected on a quartz-fiber
filter, and extracted into water using 15-mL of DDW, as described above. The anions are then
analyzed using a Dionex ICS-3000 ion chromatograph (IC; Sunnyvale, CA).6 An ion-exchange
column is used to separate the ions for individual quantification by a conductivity detector. Prior to
detection, the column effluent enters a suppressor column where the chemical composition of the
component is altered, resulting in a matrix of low conductivity. The ions are identified by their
elution/retention times and are quantified by the conductivity peak area, as compared with calibration
curves derived from solution standards.
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250-µL of filter extract is injected into the Dionex IC. The system used for anion analysis contains a
guard column (AG14 column, Cat. No. 046134) and an anion separator column (AS14 column, Cat.
No. 046129) with a strong basic anion exchange resin, and an anion micro membrane suppressor
column (250 × 4 mm ID) with a strong acid ion exchange resin. The anion eluent consists of 0.0035
M sodium carbonate (Na2CO3) and 0.001 M sodium bicarbonate (NaHCO3) prepared in DDW. The
DDW is verified to meet ATSM Type 1 specifications prior to preparation of the eluent. For
quantitative determinations, the IC is operated at a flow rate of 2.0 mL/min.
NIST traceable primary standard solutions are purchased from Environmental Research Associates
(ERA; Arvada, CO) or Dionex (Sunnyvale, CA). Calibration standards are prepared monthly by
diluting primary standard solutions to a range of concentrations expected in filter extracts. These
standards are stored in a refrigerator. The calibration concentrations prepared are at 0.05, 0.1, 0.2,
0.5, 1.0, 2.0 and 3.0 g/mL for each of the analysis species. Calibrations are performed daily.
A DDW blank is analyzed after every 20 samples and a calibration standard is analyzed after every
10 samples. These quality control checks verify the baseline and calibration, respectively. ERA
standards (ERA Wastewater Nutrient and ERA Mineral WW) are used daily as an independent
quality assurance (QA) check. If the values obtained for these standards do not coincide within a prespecified uncertainty level (typically three standard deviations of the baseline level or ±5%), the
samples analyzed between that standard and the previous calibration standards are re-analyzed.
After analysis, the printout for each sample in the batch is reviewed for the following: 1) proper
operational settings, 2) correct peak shapes and integration windows, 3) peak overlaps, 4) correct
background subtraction, and 5) quality control sample comparisons. When values for replicates differ
by more than ±10%, or values for standards differ by more than ±5%, samples before and after these
quality control checks are designated for re-analysis in a subsequent batch. Individual samples with
unusual peak shapes, background subtractions, or deviations from standard operating parameters are
also designated for re-analysis. Dionex Chromeleon software operating on a Dell Optiplex
microcomputer controls the sample throughput, calculates concentrations, and records data in the
laboratory data base. MDL is defined as 3 times the standard deviation of multiple measurements of a
laboratory blank filter.
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7. Water-Soluble Particulate Cation Analyses
Water-soluble particulate cations (NH4+, K+, Na+, Mg2+, and Ca2+) are collected on the same quartzfiber filters used for collection of particulate anions (see above), and are isolated in the same water
extract solution. Different analytical methods are then used to measure NH4+ (automated colorimetry)
and the rest of the cations (atomic absorption). These methods are described below:
a) NH4+ measurement
Ammonium concentrations are measured using the indol-phenol method with an automated
colorimetric analyzer system (Astoria Analyzer AC; Astoria Pacific, Clackamas, OR, USA). 7 The
heart of the AC system is a peristaltic pump, which introduces air bubbles into the sample stream.
Each sample is mixed with reagents and subjected to appropriate reaction periods before submission
to a colorimeter. Beer’s Law relates the liquid’s light absorbency to the concentration of the ion in
the sample. A photomultiplier tube measures this absorbency through an interference filter that is
specific to the species being measured.
Water-soluble NH4+ in the extract is reacted with phenol and alkaline sodium hypochlorite to produce
indol-phenol, a blue dye. The reaction is catalyzed by the addition of sodium nitro-prusside. The
absorbency of the solution is measured at 630 nm. Two mL of extract in a sample vial is placed in an
autosampler that is controlled by a computer. Eight standard concentrations (i.e., 0.05, 0.1, 0.2, 0.5,
1.0, 2.0, 5.0, and 10.0 µg/mL) are prepared from ACS reagent-grade (NH4)2SO4. Each set of samples
consists of two distilled water blanks to establish a baseline, seven calibration standards and a blank,
then sets of 10 samples followed by analysis of one of the standards and a replicate from a previous
batch. The system determines carry-over by analysis of a low concentration standard following a
high concentration standard. The percent carry-over is then automatically calculated and can be
applied to the samples analyzed during the run. Astoria’s FASPac software operating on a Dell
Optiplex microcomputer controls the sample throughput, calculates concentrations, and records data
in the laboratory data base.
When present in high concentrations (>20% of the NH4+ level) formaldehyde has been found to
interfere with NH4+ measurements. Hydrogen sulfide (H2S) also interferes when it is present in
concentrations that exceed 1 mg/mL. Also, NO3- and SO4= are potential interferents when present at
levels that exceed 100 times the NH4+ concentration, although these levels are rarely observed. The
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precipitation of hydroxides of heavy metals such as calcium and magnesium is also a potential
problem, but this is prevented by addition of sodium citrate/sodium potassium tartrate buffer solution
to the sample stream.
b) K+, Na+, Mg2+, and Ca2+ measurement
The remaining water-soluble cations are measured by atomic absorption (AA) spectrometry, using a
Varian SpectrAA 880 Double Beam Atomic Absorption Spectrometer (Varian, Palo Alto, CA,
USA).8 Atomic absorption methods rely on the principle that free, uncombined atoms will absorb
light at specific wavelengths corresponding to the energy requirements of the specific atom. Atoms in
the ground state absorb light and are exited into a higher energy state. Each transition between energy
states is characterized by a different energy, and therefore a different wavelength of light. The atomic
spectrum of each element comprises a number of discrete lines arising from both the ground and
exited states. The lines which originate in the ground state atoms, called resonance lines, are usually
of interest in atomic absorption spectrometry, as ground state atoms are most prevalent in practical
atomization methods.
The amount of light absorbed is proportional to the concentration of the atoms over a given
absorption path length and wavelength. Standards of known concentration are prepared, matched to
the sample matrix, and measured. The unknown sample absorbencies are compared to the
absorbencies of the standards. Since the measured absorbance is directly proportional to the
concentration of analyte, this gives a simple and accurate method of determining the unknown
concentration.
The Varian SpectrAA instrument uses a hollow-cathode lamp that emits wavelengths appropriate for
each analysis. The monochrometer is set at 766.5 nm for K+, 589 nm for Na+, 285.2 nm for Mg2+, and
422.7 nm for Ca2+. Approximately 1-2 mL of the aqueous filter extract solutions are aspirated (at 0.5
mL/min) into an air/acetylene flame within the AA spectrometer. The output of the photomultiplier is
recorded at a rate of two readings per second. These readings are averaged over 2.5-second intervals
and compared to the results from standard analyses over the same averaging times.
For routine analysis, up to 120 sample vials containing 1 mL of solution per cation analyzed are
loaded into the autosampler. Sets of 13 vials follow, with each set containing 10 filter extract
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samples, one standard, one blank, and one replicate from a previous batch. Samples are re-analyzed
when quality control standards differ from specifications by more than ±5% or when replicates (at
levels exceeding 10 times detection limits) differ by more than ±10%.
NIST traceable ICP grade standards at concentration levels of 1,000 µg/mL are used for stock
standard solutions. Stock solutions are diluted monthly for use as calibration standards. Ionization
interference is eliminated by addition of cesium chloride (CsCl) to both samples and standard
solutions. Varian SpectrAA Pro software operating on a Dell Optiplex microcomputer controls the
sample throughput, calculates concentrations, and records data in the laboratory data base. MDL is
defined as 3 times the standard deviation of multiple measurements of a laboratory blank filter.
8. Ammonia
Ammonia is collected on a citric acid impregnated cellulosic fiber filter, where it is chemically
reacted to produce ammonium citrate. The filter is then extracted with DDW, and the extract is
analyzed for ammonium ion using the indol-phenol method with an automated colorimetric analyzer
system, as described above.
9. Acid Gases
Acid gases (HCl, HNO3, and H2SO4) are collected on a cellulose fiber filter that is impregnated with
potassium carbonate (K2CO3). During collection, these acid gases react with the potassium carbonate
to produce the corresponding potassium salts (KCl, KNO3, and K2SO4). This filter is then extracted
with DDW, and the extract is analyzed for anions using the same ion chromatographic (IC) method
described above.6 In addition, sulfur dioxide (SO2) present in the gas phase reacts on the filter to
produce sulfite, which is further oxidized by hydrogen peroxide (H2O2) to sulfate before IC analysis.
Thus, the total sulfate measurement by IC represents the sum of H2SO4 and SO2 present in the
original gas sample.
10. Hydrogen Sulfide (H2S)
Hydrogen sulfide (H2S) is collected on a cellulosic fiber filter that is impregnated with silver nitrate
(AgNO3). During collection, the H2S is reacted to produce silver sulfide (Ag2S). This filter is not
extracted, but is analyzed directly by XRF, to quantify the sulfur on the filter, from which the
original H2S concentration in the sampled gas is computed.4
14
Part 2: Results from Analysis of Syngas Samples Collected from Synterra IBR
Configuration of Filter Packs used for Syngas Collection
Filter Pack No. 1
Species
Filters
Sampled
Total PM
PM Elements
Teflon
Filter Pack No. 2
Species
Filters
Sampled
OC/EC,
Carbon
Fractions
Quartz 1
HCl, HNO3,
H2SO4
NH3
K2CO3
Citric Acid
Filter Pack No. 3
Species
Filters
Sampled
Quartz 2
NH4+, K+,
Na+, Cl-,
NO3-, SO4=
H2S
AgNO3
Summary Results of Syngas Trace Contaminants Collected on Cartridges and in Canisters
(concentrations expressed as ppbv or µg/m3 in undiluted syngas)
Analytical
Method
(Sampling
Method)
GC/MS/FID
(Canister
Samples)
ppbv
GC/MS
(Tenax
Cartridges)
µg/m3
HPLC
(DNPH
Cartridges)
ppbv
Species
Measured
#5 Wood
Chips*
#6 Wood
Chips
#8 Wood
Chips
#10 Wood
Chips
before
Scrubber*
442435
827000
1566368
1458876
2877900
5802287
157919
359199
#1
Blank
#3 Rice
Hulls
#7 Wood
Chips
Acetylene
0.00
179816
856278
853185
Ethene
0.00
618851
1964919
2434249
Ethane
0.00
53304
111525
119662
71527
Propene
0.00
1365
8460
7678
518
9179
22275
1,3-butadiene
0.00
367.1
2629.8
1675.0
756.1
1766.5
5616.2
1,2-butadiene
0.00
265.8
1388.9
1270.8
554.7
1238.0
2671.4
Cyclopentene
0.00
0.00
0.00
19.69
0.00
14.87
0.00
Benzene
132.8
802395
344970
948279
871753
1630000
5845000
Toluene
0.00
43.04
102.82
194.41
214.25
663.22
3879.5
Furan
0.00
9.34
54.45
9.82
20.74
7.25
120.94
Sum of others
Styrene
0.00
0.95
0.00
20.73
0.00
50.04
0.00
4.06
0.03
27.98
0.00
51.94
0.00
4194.10
Ethylbenzene
1.05
2.18
6.41
0.43
1.99
4.26
238.31
Indene
0.07
9.59
48.78
2.23
2.56
12.23
2254.24
Naphthalene
1.87
10.34
43.84
2.14
11.86
11.44
1804.68
Formaldehyde
0.37
0.94
1.75
0.72
0.44
0.78
2.11
Acetaldehyde
0.63
82.93
102.93
479.18
511.18
428.77
365.00
Acetone
4.58
25.10
4.44
5.18
6.17
3.55
3.26
Acrolein
0.00
0.98
1.74
0.62
2.03
1.83
0.00
Propionaldehyde
0.22
0.54
0.00
1.63
1.19
0.00
0.00
2-Butanone (MEK)
0.15
6.17
3.53
6.13
6.23
17.41
6.19
Methacrolein
0.00
0.00
3.40
2.32
1.16
72.71
14.96
Benzaldehyde
0.00
0.49
7.25
2.91
2.47
8.10
9.32
Sum of Others
0.00
0.53
1.05
0.15
0.00
1.09
2.15
*Syngas dilution factors: 4.6 for Sample #5; 5.0 for Sample #10
15
Detailed Analysis of Syngas Samples
#3 Rice
Hulls
#3A Rice
Hulls
#3B Rice
Hulls
#5 Wood
Chips
#6 Wood
Chips
N/A
N/A
N/A
N/A
4.6
N/A
µg/m3
7.03
12.74
0.00
11.88
108.84
Total Organic Carbon (OC)
µg/m3
158.48
18.43
295.43
21.69
331.66
Total Elemental Carbon (EC)
µg/m3
22.39
0.12
25.58
1.57
60.08
Total Carbon
µg/m3
180.87
18.55
321.01
23.26
391.73
7.08
155.04
11.55
13.80
5.52
Species Measured
units
Gravimetry
(Teflon Filters)
Thermal Optical
(Quartz Filters)
Mass Concentration
OC/EC Ratio
Ion Chromatography
(Quartz Filter)
Automated Colorimetry
(Citric Acid Cellulose
Impregnated Filters)
Ion Chromatography
(K2CO3 Impregnated
Cellulose Filters)
X-Ray Fluorescence
(AgNO3 Impregnated Filter)
#10 Wood
#7 Wood #8 Wood
Chips before
Chips
Chips
Scrubber
#1
Blank
DF*
Analytical Method
(Sampling Method)
N/A
N/A
5.0
Chloride
µg/m3
0.00
0.00
0.00
0.00
0.55
Nitrate
µg/m3
1.87
0.87
5.32
0.55
4.84
Sulfate
µg/m3
1.79
0.40
2.45
0.35
4.43
Ammonium (NH4+)
µg/m3
5.59
0.93
16.25
0.90
11.94
Sodium (Na+)
µg/m3
0.80
0.54
0.00
0.00
0.00
Potassium (K+)
µg/m3
4.82
0.67
1.38
0.12
5.33
NH3
µg/m3
33.43
35.35
200.60
24.17
120.82
HCl
µg/m3
N/A
N/A
N/A
N/A
HNO3
µg/m3
15.27
2.62
31.97
3.08
91.02
SO2
µg/m3
H2SO4
µg/m3
0.00
5.74
0.00
0.00
1798.15
H2S
µg/m3
0.00
0.53
0.00
767.1
* DF = Dilution Factor
16
N/A
N/A
N/A
N/A
N/A
Analytical Method
(Sampling Method)
GC/MS/FID
(Canister Samples)
DF*
#1 Blank
Species Measured
units
#3 Rice
Hulls
#3A Rice
Hulls
#3B Rice
Hulls
#5 Wood
Chips
#6 Wood
Chips
#7 Wood
Chips
#8 Wood
Chips
#10 Wood
Chips before
Scrubber
N/A
N/A
N/A
N/A
4.6
N/A
N/A
N/A
5.0
Acetylene
ppbv
0.00
179816.52
5235.24
8562.52
856278.71
853185.85
442435.16
827000.25
1566368.75
Ethene
ppbv
0.00
618851.00
43255.88
74225.23 1964919.90 2434249.75 1458876.25 2877900.25
5802287.50
Ethane
ppbv
0.00
53304.59
4524.99
9152.21
111525.18
119662.25
71527.15
157919.31
359199.68
propene
ppbv
0.00
1365.35
178.55
235.94
8460.26
7678.27
518.39
9179.04
22275.23
propane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,3-butadiene
ppbv
0.00
367.12
0.00
326.92
2629.82
1674.96
756.15
1766.47
5616.16
1-butene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
c-2-butene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
isobutene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
t-2-butene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-butane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
iso-butane
ppbv
0.00
977.39
0.00
0.00
0.00
0.00
0.00
0.00
0.00
iso-pentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-pentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,2-butadiene
ppbv
0.00
265.80
0.00
0.00
1388.97
1270.80
554.76
1238.03
2671.44
2,2,4-trimethylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-methyl-1-butene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1-pentene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
isoprene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
t-2-pentene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-methyl-2-butene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
c-2-pentene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,2-dimethylbutane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
cyclopentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
cyclopentene
ppbv
0.00
0.00
0.00
0.00
0.00
19.69
0.00
14.87
0.00
2,3-dimethylbutane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
26.73
0.00
0.00
2-methylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-methyl-1-pentene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3-methylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
t-2-hexene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-hexane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
c-2-hexene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,3-hexadiene (trans)
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
17
DF*
Analytical Method
(Sampling Method)
GC/MS/FID
(Canister Samples)
#1 Blank
Species Measured
units
#3 Rice
Hulls
#3A Rice
Hulls
#3B Rice
Hulls
#5 Wood
Chips
#6 Wood
Chips
#7 Wood
Chips
#8 Wood
Chips
#10 Wood
Chips before
Scrubber
N/A
N/A
N/A
N/A
4.6
N/A
N/A
N/A
5.0
methylcyclopentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,4-dimethylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
benzene
ppbv
132.83
cyclohexane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
cyclohexene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-methylhexane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,3-dimethylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,3-dimethylcyclopentane (cis)
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3-methylhexane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-heptane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,3-dimethyl-2-pentene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
methylcyclohexane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,3,4-trimethylpentane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-methylheptane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
4-methylheptane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3-methylheptane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-octane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Toluene
ppbv
0.00
43.04
137.60
150.58
102.82
194.41
214.25
663.22
3879.46
m&p-xylene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
styrene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o-xylene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-nonane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
isopropylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3-ethyltoluene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-propylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
4-ethyltoluene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
alpha-pinene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,3,5-trimethylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
o-ethyltoluene
1,2,4-trimethylbenzene+tbutylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-decane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
indan
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,2,3-trimethylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
802395.94 428961.25 422706.13 344970.53
18
948279.75
871753.88 1630000.00
5845000.00
DF*
Analytical Method
(Sampling Method)
GC/MS/FID
(Canister Samples)
GC/MS
(Tenax Cartridges)
HPLC
(DNPH Cartridges)
#1 Blank
Species Measured
units
#3 Rice
Hulls
#3A Rice
Hulls
#3B Rice
Hulls
#5 Wood
Chips
#6 Wood
Chips
#7 Wood
Chips
#8 Wood
Chips
#10 Wood
Chips before
Scrubber
N/A
N/A
N/A
N/A
4.6
N/A
N/A
N/A
5.0
1,3-diethylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
1,4-diethylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-butylbenzene
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
n-undecane
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
furan
ppbv
0.00
9.34
12.98
5.22
54.45
9.82
20.74
7.25
120.94
2-methyl-furan
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-furfural
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
3-furfural
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2,5-dimethyl-furan
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-ethyl-furan
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
styrene
µg/m3
0.95
20.73
43.34
9.85
50.04
4.06
27.98
51.94
4194.10
ethylbenzene
µg/m3
1.05
2.18
4.79
0.82
6.41
0.43
1.99
4.26
238.31
Indene
µg/m3
0.07
9.59
6.85
12.13
48.78
2.23
2.56
12.23
2254.24
naphthalene
µg/m3
1.87
10.34
2.88
6.26
43.84
2.14
11.86
11.44
1804.68
Formaldehyde
ppbv
0.37
0.94
0.39
0.72
1.75
0.72
0.44
0.78
2.11
Acetaldehyde
ppbv
0.63
82.93
38.61
27.53
102.93
479.18
511.18
428.77
365.00
Acetone
ppbv
4.58
25.10
5.68
5.42
4.44
5.18
6.17
3.55
3.26
Acrolein
ppbv
0.00
0.98
0.00
0.00
1.74
0.62
2.03
1.83
0.00
Propionaldehyde
ppbv
0.22
0.54
0.47
0.20
0.00
1.63
1.19
0.00
0.00
Crotonaldehyde
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
2-Butanone (MEK)
ppbv
0.15
6.17
2.85
1.82
3.53
6.13
6.23
17.41
6.19
Methacrolein
ppbv
0.00
0.00
0.00
0.00
3.40
2.32
1.16
72.71
14.96
n-Butyraldehyde
ppbv
0.00
0.11
0.00
0.00
0.11
0.15
0.00
0.00
0.00
Benzaldehyde
ppbv
0.00
0.49
0.00
0.17
7.25
2.91
2.47
8.10
9.32
Valeraldehyde
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
Glyoxal
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
m-Tolualdehyde
ppbv
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.15
Hexaldehyde
ppbv
0.00
0.42
0.44
0.00
0.93
0.00
0.00
1.09
2.01
19
Analytical Method
(Sampling Method)
X-Ray Fluorescence
(Teflon Filters)
DF*
#1 Blank
Species Measured
units
#3 Rice
Hulls
#3A Rice
Hulls
#3B Rice
Hulls
N/A
N/A
#5 Wood
Chips
#6 Wood
Chips
#7 Wood
Chips
#8 Wood
Chips
N/A
N/A
#10 Wood
Chips before
Scrubber
N/A
N/A
4.6
N/A
Sodium
µg/m3
0.00
1.45
59.18
1.95
22.91
Magnesium (Mg)
µg/m3
0.00
0.09
13.26
0.33
0.00
Aluminum (Al)
µg/m3
3.72
0.87
10.12
0.18
6.73
Silicon (Si)
µg/m3
0.02
0.12
2.82
0.02
0.16
Phosphorus (P)
µg/m3
0.00
0.00
0.00
0.00
0.00
Sulfur (S)
µg/m3
0.00
0.00
0.00
0.00
1.14
Chlorine (Cl)
µg/m3
0.04
0.37
0.49
0.07
1.05
Potassium
µg/m3
0.03
0.44
0.99
0.05
0.03
Calcium (Ca)
µg/m3
0.00
0.04
1.22
0.06
0.00
Scandium (Sc)
µg/m3
0.00
0.42
8.86
0.25
0.40
Titanium (Ti)
µg/m3
0.16
0.00
0.11
0.06
0.00
Vanadium (V)
µg/m3
0.06
0.00
0.00
0.00
0.00
Chromium (Cr)
µg/m3
0.00
0.01
0.00
0.01
0.25
Manganese (Mn)
µg/m3
0.00
0.03
0.00
0.00
0.15
Iron (Fe)
µg/m3
0.00
0.01
0.00
0.08
0.08
Cobalt (Co)
µg/m3
0.00
0.00
0.00
0.00
0.05
Nickel (Ni)
µg/m3
0.00
0.01
0.00
0.00
0.00
Copper (Cu)
µg/m3
0.00
0.00
0.05
0.01
0.12
Zinc (Zn)
µg/m3
0.00
0.01
0.23
0.07
6.20
Gallium (Ga)
µg/m3
0.02
0.05
0.00
0.00
0.00
Arsenic (As)
µg/m3
0.00
0.00
0.00
0.00
0.00
Selenium (Se)
µg/m3
0.00
0.00
0.00
0.00
0.00
Bromine (Br)
µg/m3
0.16
0.00
0.22
0.03
0.00
Rubidium (Rb)
µg/m3
0.00
0.00
0.00
0.00
0.61
Strontium (Sr)
µg/m3
0.00
0.02
0.08
0.02
0.60
Yttrium (Y)
µg/m3
0.13
0.00
0.00
0.00
0.35
Zirconium (Zr)
µg/m3
0.00
0.00
0.00
0.00
0.00
Niobium (Nb)
µg/m3
0.00
0.00
0.00
0.00
0.00
Molybdenum (Mo)
µg/m3
0.00
0.00
0.00
0.00
0.00
Palladium (Pd)
µg/m3
0.00
0.00
0.00
0.03
0.00
Silver (Ag)
µg/m3
0.02
0.00
0.44
0.00
0.00
Cadmium (Cd)
µg/m3
Indium (In)
µg/m3
0.00
0.00
0.00
0.00
0.35
0.00
0.03
0.00
0.16
0.00
20
5.0
Analytical Method
(Sampling Method)
DF*
Species Measured
units
#3A Rice
Hulls
#3B Rice
Hulls
#5 Wood
Chips
#6 Wood
Chips
#7 Wood
Chips
#8 Wood
Chips
N/A
N/A
4.6
0.28
N/A
0.00
N/A
N/A
#10 Wood
Chips before
Scrubber
Tin (Sn)
µg/m3
N/A
0.00
N/A
0.00
Antimony (Sb)
µg/m3
0.00
0.00
0.45
0.00
0.00
µg/m3
0.00
0.00
0.00
0.00
0.00
Barium (Ba)
µg/m3
0.00
0.40
0.00
0.00
0.00
Lanthanum (La)
µg/m3
2.38
0.18
0.00
0.36
0.00
Cerium (Ce)
µg/m3
0.00
0.03
0.00
0.00
0.00
Samarium (Sm)
µg/m3
0.00
0.00
3.10
0.50
12.66
Europium (Eu)
µg/m3
2.73
0.00
5.73
0.00
2.40
Terbium (Tb)
µg/m3
0.00
0.00
0.00
0.42
0.00
Hafnium (Hf)
µg/m3
0.65
0.00
2.93
0.00
1.54
Tantalum (Ta)
µg/m3
0.00
0.00
0.79
0.08
0.16
Tungsten (W)
µg/m3
0.00
0.00
0.00
0.00
2.04
Iridium (Ir)
µg/m3
0.00
0.00
0.00
0.02
0.00
Gold (Au)
µg/m3
0.00
0.07
0.00
0.02
0.00
Mercury (Hg)
µg/m3
0.00
0.00
0.00
0.00
0.00
µg/m3
0.00
0.00
0.00
0.00
0.31
Lead (Pb)
µg/m3
0.02
0.00
0.87
0.01
0.08
Uranium (U)
µg/m3
0.29
0.00
0.59
0.00
0.36
Cesium (Cs)
X-Ray Fluorescence
(Teflon Filters)
#1 Blank
#3 Rice
Hulls
Thallium (Tl)
21
5.0
0.00
Reference List
1. U.S.EPA Office of R&D, National Risk Management Research Laboratory, and Center for
Environmental Research Information; Method TO-15: Determination of Volatile Organic Compounds
(VOCs) in Air Collected in Specially-Prepared Canisters and Analyzed by Gas Chromatography Mass
Spectrometry (GC/MS). Compendium of Methods for the Determination of Toxic Organic Compounds
in Ambient Air. U.S. EPA Office of Research and Development, Cincinnati, OH. 1999.
2. Zielinska, B., J. Sagebiel, G. Harshfield, and R. Pasek; Volatile Organic Compound Measurements in
the California/Mexico Border Region During SCOS97. Science of the Total Environment, 276, (1-3), 1931. 2001.
3. Zielinska, B., J. C. Sagebiel, G. Harshfield, A. W. Gertler, and W. R. Pierson; Volatile Organic
Compounds Up to C-20 Emitted From Motor Vehicles; Measurement Methods. Atmospheric
Environment, 30, (12), 2269-2286. 1996.
4. Watson, J. G., J. C. Chow, and C. A. Frazier; Chapter 2: X-Ray Fluorescence Analysis of Ambient Air
Samples. Elemental Analysis of Airborne Particles, Vol. 1. Landsberger, S. and M. Creatchman, editors.
Gordon and Breach Science, Amsterdam. 1999.
5. Chow, J. C., J. G. Watson, L. C. Pritchett, W. R. Pierson, C. A. Frazier, and R. G. Purcell; The DRI
Thermal Optical Reflectance Carbon Analysis System - Description, Evaluation and Applications in
United-States Air-Quality Studies. Atmospheric Environment Part A-General Topics, 27, (8), 11851201. 1993.
6. U.S.EPA; Method 300.0, Determination of Inorganic Anions by Ion Chromatography. Environmental
Monitoring Systems Laboratory, Office of Research and Development, 1993.
7. U.S.EPA; Method 350.1: Determination of Ammonia Nitrogen by Semi-Automated Colorimetry.
Environmental Monitoring Systems Laboratory, Office of Research and Development, 1993.
8. U.S.EPA; EPA Method 3111: Standard Methods for the Examination of Water and Wastewater. 1995.
22